CN108219335A - A kind of high durable polyphenylene oxide/acrylonitrile-acrylate-styrene alloy material and preparation method thereof - Google Patents
A kind of high durable polyphenylene oxide/acrylonitrile-acrylate-styrene alloy material and preparation method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/285—Feeding the extrusion material to the extruder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
- C08K2003/3036—Sulfides of zinc
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Abstract
The present invention relates to a kind of high durable polyphenylene oxide/acrylonitrile acrylate styrene alloy material and preparation method thereof, which includes 30 70 parts by weight of polyphenylene oxide resin, 20 50 parts by weight of acrylonitrile acrylate styrene resin, 6 30 parts by weight of HIPS resins, 2 10 parts by weight of compatilizer, 2 10 parts by weight of toughener, 0.1 1 parts by weight of antioxidant, 0.3 2.0 parts by weight of light stabilizer, 0.1 2.0 parts by weight of lubricant, 0.1 1 parts by weight of sulfide, 0.1 1 parts by weight of oxide；The lubricant is linear low density polyethylene.The alloy material remains the distinctive high temperature resistant of polyphenyl ether material, resistant to chemical etching, high-mechanical property, electrical property advantage and the excellent weatherability of acrylonitrile acrylate styrene materials, solvent resistance advantage, the shortcomings of acrylonitrile acrylate styrene poor heat resistance, cold resistance are poor and polyphenylene oxide melt viscosity is excessive, weatherability is poor, poor solvent resistance is overcome simultaneously, increases the application field of polyphenyl ether material.
Description
Technical field
The present invention relates to technical field of alloy material, especially a kind of high durable polyphenylene oxide/acrlylonitrile-acrylate-benzene
Ethylene alloy material and preparation method thereof.
Background technology
Polyphenylene oxide (English name：Polyphenylene oxide, abbreviation PPO) it is one of five big general engineering plastic of the world,
It is a kind of thermoplastic engineering plastic haveing excellent performance.It has rigidity is big, heat resistance is high, fire retardant, intensity is higher, it is wear-resisting, nontoxic,
The advantages that anti-pollution.The dielectric constant and dielectric loss of PPO is one of minimum kind in engineering plastics, hardly by temperature
The influence of degree, humidity.But the light resistance of PPO materials is poor, is used under sunlight or fluorescent lamp for a long time, product jaundice easy to change,
Be not suitable in outdoor long-time service, the reason is that ultraviolet light can make ether bond rupture in PPO strands；Another disadvantage is that mobility
Difference, processing forming is very poor, and pure PPO resins cannot use injecting method to be molded, and this is mainly due to PPO molecule chain rigidities
Greatly, for melt flows close to Newtonian fluid, melt viscosity is big, is influenced very little by shear rate.These two aspects significantly impacts PPO
The popularization and application of material.PPO/PS is prepared using the compatibility blending of PPO and polystyrene (PS) in broad compositing range to close
Gold solves the disadvantage that PPO material melt viscosities are big, while improves PPO materials notch sensitive, the problem of impact strength is low,
But PS cannot improve the weather-proof problem of PPO materials, the light resistance of PPO/PS alloys is still very poor.
Acrylonitrile-acrylate-styrene (ASA) resin is due to introducing not double bond containing acrylic rubber, only wave
The long light less than 300nm can just play it influence of aging, therefore weatherability is preferable, is chronically exposed to ultraviolet light or sunlight
Under, it can also keep mechanical performance and the stability of appearance color.
The weather-proof modification of current polyphenylene oxide is mainly realized by adding weather resisting agent, but weather resisting agent modified effect is paid no attention to
Think, and with timeliness, alloying is a kind of polyphenyl ether modified preferable method, still, poly- there is presently no being effectively improved
The alloy material of phenylate weatherability.
Invention content
The present invention for existing polyphenyl ether material weatherability it is poor the problem of, provide a kind of high durable polyphenylene oxide/acrylonitrile-
Acrylate-styrene bipolymer alloy material, the alloy remain the distinctive high temperature resistant of polyphenyl ether material, resistant to chemical etching, high machinery
Performance, electrical property advantage and the excellent weatherability of acrylonitrile-acrylate-styrene material, solvent resistance advantage, overcome simultaneously
Acrylonitrile-acrylate-styrene poor heat resistance, cold resistance difference and polyphenylene oxide melt viscosity is excessive, weatherability is poor, resistance to molten
The shortcomings of agent is poor, the alloy material have the advantages that good weather resistance, good toughness, processing performance is excellent, intensity is high.
The present invention is realized using following technical solution：
A kind of high durable polyphenylene oxide/acrylonitrile-acrylate-styrene alloy material includes the raw material of following parts by weight
Component：
The lubricant is linear low density polyethylene.
Further, the polyphenylene oxide resin is 30-50 parts by weight；Acrylonitrile-acrylate-styrene resin is 24-
28 parts by weight；HIPS resins are 9 parts by weight.
Further, the compatilizer is styrene/acrylonitrile copolymer graft glycidyl methacrylate
(SAN-g-GMA), styrene-grafted maleic anhydride (PS-g-MAH), ABS grafted maleic anhydrides (ABS-g-MAH) or polyphenylene oxide connect
One or more of branch maleic anhydride (PPO-g-MAH).
Further, the toughener is styrene block copolymer.
Further, the styrene block copolymer is Styrene-Butadiene-Styrene Block Copolymer, benzene second
Alkene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, styrene-ethylene-the third
One or more of alkene-styrene type block copolymer.
Further, the lubricant is calcium stearate, silicone, paraffin, polyethylene wax, zinc stearate or polyethylene
At least one of.
Further, the polyethylene is linear low density polyethylene.
Further, the inherent viscosity of the polyphenylene oxide resin is 0.3-0.55dl/g；The melting means of the HIPS resins
It is 5-20g/10min (200 DEG C, 5kg), 60-150J/m.
Further, the antioxidant is four [β-(3,5 di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters
(antioxidant 1010), β-(- 4- hydroxyls -3,5 di-tert-butyl-phenyl) positive octadecyl of propionic acid (antioxidant 1076), phosphorous acid three
Any one of (2,4 di-tert-butyl-phenyl) ester (irgasfos 168) is several.
Further, the light stabilizer is N, bis- (2,2,2,6- tetramethyl -4- piperidyls) -1, the 6- hexamethylene diamines of N-,
One kind of the double -2,2,6,6- tetramethyl -4- piperidines alcohol esters of 2-hydroxy-4-n-octoxybenzophenone or decanedioic acid or it is a kind of with
On.
Further, the oxide is one or more of zinc oxide, magnesia, calcium oxide；The sulfide
It is one or more of zinc sulphide, magnesium sulfide.
A kind of preparation method of high durable polyphenylene oxide/acrylonitrile-acrylate-styrene alloy material, including walking as follows
Suddenly：Each raw material is weighed according to said ratio, and wherein polyphenylene oxide resin is mixed from the side feeding blanking of double screw extruder, other raw materials
From the main feeding blanking of double screw extruder after closing uniformly.The processing temperature of double screw extruder is 230~270 DEG C, and screw rod turns
Speed is 500~600r/min, and the draw ratio of double screw extruder is 48:1.
The invention has the advantages that：
1. the present invention is using linear low density polyethylene as lubricant, material more preferable to the lubricant effect of PPO/ASA alloys
Material dispersibility is more preferable, mechanical performance higher, and the weatherability of material is more preferable；Linear low density polyethylene can be precipitated after adding in simultaneously
Play the role of releasing agent to material table, material injection made easily to be demoulded when being molded, accelerate injection beat, reduce molding cycle,
Production efficiency is improved, since linear low density polyethylene is high polymer, the injection defects such as gas trace, energy will not be generated by precipitateing into surface
Enough improve the first-time qualification rate of product.
2. the present invention using inherent viscosity 0.30~0.55dl/g polyphenylene oxide resin, can make material impact strength and
Mobility is balanced；Used rubber phase acrylate content is that 30~70% ASA resin can improve the weatherability of material
Energy and anti-aging property improve the processing fluidity of material, improve the solvent craze problem of polyphenylene oxide resin in itself；It is used
Compatilizer can effectively improve the interface binding power of polyphenylene oxide resin and ASA resin between the two, increase the compatibility of storeroom, improve
The mechanical performance of alloy material；Used antioxidant can effectively block, inhibit or delay polymer oxidation or autoxidation
Process improves the anti-aging property during composite material antioxygenic property in process and use；Used light
Stabilizer can effectively absorb ultraviolet light, Trapped free radical, improve the weather resistance of material；Used lubricant can have
Effect reduce between resin and resin and the frictional force between resin and equipment, reduce melt viscosity, improve the mobility of material
And processing performance, while lubricant moves to material surface, reduces the bonding force between material and mold, taking off when being conducive to injection
Mould plays the role of releasing agent；Used sulfide and oxide can improve the CTI and weatherability of material, anti-with catalyst
Should, inhibit decomposition of the material in process.
3. the present invention when using twin-screw extrusion by the way of the feeding of PPO sides, after other raw materials are fully plasticized again
PPO materials are added in, dispersibility preferably, using slightly strong combination is sheared, makes raw material fully dispersed, so as to ensure material between making raw material
Stable quality, while the present invention using draw ratio be 48:1 double screw extruder extrusion plastic particle, resin is in extruder
The middle residence time is moderate, PPO materials and other materials is made to be sufficiently mixed uniformly, the weather resistance of product is best, the particle of extrusion
Common injection molding machine injection molding product can be used whenever and wherever possible, and overcoming double-layer coextrusion needs special equipment, material straight
The drawbacks of being connected into type and simple product；The PPO/ASA alloy materials that are prepared are at low cost, good toughness, processing performance are excellent, strong
Degree is high, weather resistance is good, composite material is environmentally friendly, and heat resistance is high, mobility is high, and comprehensive performance is balanced, can be widely applied to electronics
The field of electronics such as the shell of product, the glue filling box of computerized control system.
Specific embodiment
In order to which the above objects, features and advantages of the present invention is more clearly understood, with reference to embodiment to this
Invention is described further
The preparation of 1 PPO/ASA alloy materials of embodiment
The inherent viscosity of PPO resins is 0.3-0.55dl/g, and ASA resin is copolymerized for acrylonitrile-styrene-acrylic ester
Object, rubber phase acrylate content are high flowing high-impact polystyrene for 30~70%, HIPS resins, and melting means is 5-20g/
10min (200 DEG C, 5kg), 60-150J/m.Toughener is styrene-ethylene-butylene-styrene block copolymer, and antioxidant is
Antioxidant 1010 and 168, lubricant are linear low density polyethylene LLDPE, and sulfide is zinc sulphide, and oxide is zinc oxide.
Each raw material components are weighed by following weight percent content：PPO 30kg, polystyrene 9kg, ASA 50kg, toughening
Agent 3.5kg, antioxidant 0.5kg, lubricant 1kg, zinc sulphide 0.5kg, zinc oxide 0.5kg.Each raw material weighed up is put into mixing
In machine, 200r/min mixing 2min, discharging, then with double screw extruder extruding pelletization；The double screw extruder adds
Work temperature is 220~250 DEG C, and extruder includes seven warm areas, wherein one section 220 DEG C, two sections 240 DEG C, three sections 250 DEG C, four sections
250 DEG C, five sections 250 DEG C, six sections 245 DEG C, seven sections 245 DEG C, screw speed 600r/min.
The preparation of 2 PPO/ASA alloy materials of embodiment
The inherent viscosity of PPO resins is 0.3-0.55dl/g, and ASA resin is copolymerized for acrylonitrile-styrene-acrylic ester
Object, rubber phase acrylate content are high flowing high-impact polystyrene for 30~70%, HIPS resins, and melting means is 5-20g/
10min (200 DEG C, 5kg), 60-150J/m.Toughener is styrene-ethylene-butylene-styrene block copolymer, and antioxidant is
Antioxidant 1010 and 168, lubricant are linear low density polyethylene LLDPE, and sulfide is zinc sulphide, and oxide is zinc oxide.
Each raw material components are weighed by following weight percent content：PPO 50kg, polystyrene 9kg, ASA 30kg, toughening
Agent 3.5kg, antioxidant 0.5kg, lubricant 1kg, zinc sulphide 0.5kg, zinc oxide 0.5kg.Each raw material weighed up is put into mixing
In machine, 200r/min mixing 2min, discharging, then with double screw extruder extruding pelletization；The double screw extruder adds
Work temperature is 220~250 DEG C, and extruder includes seven warm areas, wherein one section 220 DEG C, two sections 240 DEG C, three sections 250 DEG C, four sections
250 DEG C, five sections 250 DEG C, six sections 245 DEG C, seven sections 245 DEG C, screw speed 600r/min.
The preparation of 3 PPO/ASA alloy materials of embodiment
The inherent viscosity of PPO resins is 0.3-0.55dl/g, and ASA resin is copolymerized for acrylonitrile-styrene-acrylic ester
Object, rubber phase acrylate content are high flowing high-impact polystyrene for 30~70%, HIPS resins, and melting means is 5-20g/
10min (200 DEG C, 5kg), 60-150J/m.Toughener is styrene-ethylene-butylene-styrene block copolymer, and antioxidant is
Antioxidant 1010 and 168, lubricant are linear low density polyethylene LLDPE, and sulfide is zinc sulphide, and oxide is zinc oxide.
Each raw material components are weighed by following weight percent content：PPO 70kg, polystyrene 9kg, ASA 10kg, toughening
Agent 3.5kg, antioxidant 0.5kg, lubricant 1kg, zinc sulphide 0.5kg, zinc oxide 0.5kg.Each raw material weighed up is put into mixing
In machine, 200r/min mixing 2min, discharging, then with double screw extruder extruding pelletization；The double screw extruder adds
Work temperature is 220~250 DEG C, and extruder includes seven warm areas, wherein one section 220 DEG C, two sections 240 DEG C, three sections 250 DEG C, four sections
250 DEG C, five sections 250 DEG C, six sections 245 DEG C, seven sections 245 DEG C, screw speed 600r/min.
The preparation of 4 PPO/ASA alloy materials of embodiment
The inherent viscosity of PPO resins is 0.3-0.55dl/g, and ASA resin is copolymerized for acrylonitrile-styrene-acrylic ester
Object, rubber phase acrylate content are high flowing high-impact polystyrene for 30~70%, HIPS resins, and melting means is 5-20g/
10min (200 DEG C, 5kg), 60-150J/m.Compatilizer is styrene-grafted maleic anhydride (PS-g-MAH), and toughener is benzene second
Alkene-ethylene-butylene, Styrene block copolymer, antioxidant are antioxidant 1010 and 168, and lubricant is linear low density polyethylene
Alkene LLDPE, sulfide are zinc sulphide, and oxide is zinc oxide.
Each raw material components are weighed by following weight percent content：PPO 50kg, polystyrene 9kg, ASA 27kg is compatible
Agent 3kg, toughener 3.5kg, antioxidant 0.5kg, lubricant 1kg, zinc sulphide 0.5kg, zinc oxide 0.5kg.Each original that will be weighed up
Material is put into mixing machine, 200r/min mixing 2min, discharging, then with double screw extruder extruding pelletization；The twin-screw
The processing temperature of extruder is 220~250 DEG C, and extruder includes seven warm areas, wherein one section 220 DEG C, two sections 240 DEG C, three sections
250 DEG C, four sections 250 DEG C, five sections 250 DEG C, six sections 245 DEG C, seven sections 245 DEG C, screw speed 600r/min.
The preparation of 5 PPO/ASA alloy materials of embodiment
The inherent viscosity of PPO resins is 0.3-0.55dl/g, and ASA resin is copolymerized for acrylonitrile-styrene-acrylic ester
Object, rubber phase acrylate content are high flowing high-impact polystyrene for 30~70%, HIPS resins, and melting means is 5-20g/
10min (200 DEG C, 5kg), 60-150J/m.Compatilizer is styrene-grafted maleic anhydride (PS-g-MAH), and toughener is benzene second
Alkene-ethylene-butylene, Styrene block copolymer, antioxidant are antioxidant 1010 and 168, and light stabilizer is ultra-violet absorber
UV-234 and hindered amine stabilizer 5411, lubricant are linear low density polyethylene LLDPE, and sulfide is zinc sulphide, oxide
It is zinc oxide.
Each raw material components are weighed by following weight percent content：PPO 50kg, polystyrene 9kg, ASA 26kg is compatible
Agent 3kg, toughener 3.5kg, antioxidant 0.5kg, light stabilizer 1kg, lubricant 1kg, zinc sulphide 0.5kg, zinc oxide 0.5kg.
Each raw material weighed up is put into mixing machine, 200r/min mixing 2min, discharged, then with double screw extruder extruding pelletization；
The processing temperature of the double screw extruder is 220~250 DEG C, and extruder includes seven warm areas, wherein one section 220 DEG C, two
240 DEG C of section, three sections 250 DEG C, four sections 250 DEG C, five sections 250 DEG C, six sections 245 DEG C, seven sections 245 DEG C, screw speed 600r/min.
The preparation of 6 PPO/ASA alloy materials of embodiment
The inherent viscosity of PPO resins is 0.3-0.55dl/g, and ASA resin is copolymerized for acrylonitrile-styrene-acrylic ester
Object, rubber phase acrylate content are high flowing high-impact polystyrene for 30~70%, HIPS resins, and melting means is 5-20g/
10min (200 DEG C, 5kg), 60-150J/m.Compatilizer is styrene-grafted maleic anhydride (PS-g-MAH), and toughener is benzene second
Alkene-ethylene-butylene, Styrene block copolymer, antioxidant are antioxidant 1010 and 168, and light stabilizer is ultra-violet absorber
UV-234 and hindered amine stabilizer 5411, lubricant are linear low density polyethylene LLDPE, and sulfide is zinc sulphide, oxide
It is zinc oxide.
Each raw material components are weighed by following weight percent content：PPO 50kg, polystyrene 9kg, ASA 24.5kg, phase
Hold agent 3kg, toughener 3.5kg, antioxidant 1kg, light stabilizer 2kg, lubricant 1kg, zinc sulphide 0.5kg, zinc oxide 0.5kg.
Each raw material weighed up is put into mixing machine, 200r/min mixing 2min, discharged, then with double screw extruder extruding pelletization；
The processing temperature of the double screw extruder is 220~250 DEG C, and extruder includes seven warm areas, wherein one section 220 DEG C, two
240 DEG C of section, three sections 250 DEG C, four sections 250 DEG C, five sections 250 DEG C, six sections 245 DEG C, seven sections 245 DEG C, screw speed 600r/min.
The preparation of 7 PPO/ASA alloy materials of embodiment
The inherent viscosity of PPO resins is 0.3-0.55dl/g, and ASA resin is copolymerized for acrylonitrile-styrene-acrylic ester
Object, rubber phase acrylate content are high flowing high-impact polystyrene for 30~70%, HIPS resins, and melting means is 5-20g/
10min (200 DEG C, 5kg), 60-150J/m.Compatilizer is styrene-grafted maleic anhydride (PS-g-MAH), and toughener is benzene second
Alkene-ethylene-butylene, Styrene block copolymer, antioxidant are antioxidant 1010 and 168, and light stabilizer is ultra-violet absorber
UV-234 and hindered amine stabilizer 5411, lubricant are linear low density polyethylene LLDPE, and sulfide is zinc sulphide, oxide
It is zinc oxide.
Each raw material components are weighed by following weight percent content：PPO 50kg, polystyrene 9kg, ASA 24.5kg, phase
Hold agent 3kg, toughener 3.5kg, antioxidant 1kg, light stabilizer 2kg, lubricant linear low density polyethylene 1kg, zinc sulphide
0.5kg, zinc oxide 0.5kg.Each raw material weighed up is put into mixing machine, 200r/min mixing 2min, discharged, then with double spiral shells
Bar extruder extruding pelletization；The processing temperature of the double screw extruder is 220~250 DEG C, and extruder includes seven warm areas,
Wherein one section 220 DEG C, two sections 240 DEG C, three sections 250 DEG C, four sections 250 DEG C, five sections 250 DEG C, six sections 245 DEG C, seven sections 245 DEG C, spiral shell
Bar rotating speed 600r/min.
The composition of raw materials of the MPPO composite materials of 1 embodiment 1-7 of table
| Material name | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| PPO(kg) | 30 | 50 | 70 | 50 | 50 | 50 | 50 |
| HIPS(kg) | 10 | 10 | 9 | 9 | 9 | 9 | 9 |
| ASA(kg) | 49 | 29 | 10 | 27 | 26 | 24.5 | 24.5 |
| Compatilizer (kg) | 0 | 0 | 0 | 3 | 3 | 3 | 3 |
| Toughener (kg) | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 |
| Antioxidant (kg) | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 1 | 1 |
| Light stabilizer (kg) | 0 | 0 | 0 | 0 | 1 | 2 | 2 |
| Lubricant (kg) | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| Oxide (kg) | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Sulfide (kg) | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
The MPPO composite materials that embodiment 1-6 is prepared are tested for the property, test result is as shown in table 2.
The performance test results of MPPO composite materials are made in 2 embodiment 1-6 of table
With reference to Tables 1 and 2, from embodiment 1-3 it is found that the increase of PPO additive amounts makes tensile strength, the bending strength of material
Become larger, impact strength increases, and mechanical performance increases, and heat distortion temperature improves, and the heat resistance of material increases, and melting means reduces, flowing
Property decline；The addition of ASA materials reduces the unsaturated bond in intermingling material system simultaneously, and it is ultraviolet to enhance intermingling material resistance
The ability of line, therefore value of chromatism reduces with the increase of ASA contents before and after colour table under ultraviolet light irradiation；But ASA materials
It is incompatible with PPO, therefore will appear lamination after two kinds of material extrusion moldings, in example 3 lamination slightly mainly by
It is less in ASA additions.After from embodiment 4 and embodiment 3 it is found that being added to compatilizer, the interface binding power of PPO and ASA increase
By force, compatibility increases, therefore the tensile strength of material, bending strength become larger, and impact strength increases, and mechanical performance increases, thermal change
Shape temperature improves, and melting means is in a slight decrease；Simultaneously because the compatibility of PPO and ASA increases, the weatherability of material improves, ultraviolet light
Colour table aberration after pre-irradiation reduces.The compatilizer one end selected in the present invention is the highly polar group such as GMA or MAH, and PPO divides
Contain ehter bond in minor structure, be polar group, therefore GMA or MAH can be very good to combine with PPO；The other end of compatilizer
It is that PS, SAN, ABS etc. contain acrylonitrile-styrene group, therefore can have good compatibility with ASA resin, compatilizer exists
Bridge beam action is played between PPO and ASA, by both PPO and ASA combination, improves the interface knot between PPO and ASA resin
With joint efforts, so as to improve the compatibility of PPO and ASA.From embodiment 4-6 it is found that in formula system add light stabilizer and
Aberration of the material before and after ultraviolet irradiation can effectively be reduced by increasing the number of antioxidant, improve the weatherability of material, this is main
It is since light stabilizer can absorb ultraviolet light, captures free radical, prevent oxidation reaction, and antioxidant can effectively prevent material
Thermal oxide.From embodiment 6-7 it is found that compared with other lubricants, linear low density polyethylene is to the profit of PPO/ASA alloys
Sliding effect is more preferable, and material scatter is more preferable, mechanical performance higher, and the weatherability of material is more preferable.Linear low density polyethylene simultaneously
Material table can be precipitate into after addition and plays the role of releasing agent, material injection is made easily to be demoulded when being molded, accelerates injection beat,
Reduce molding cycle, improve production efficiency, play additional effect, be high poly- this is mainly due to linear low density polyethylene
Object, the injection defects such as gas trace will not be generated by precipitateing into surface, and other lubricants are small-molecule substances, precipitate into surface and play profit
The injection defects such as gas trace are generated while sliding effect.The present invention using inherent viscosity 0.30~0.55dl/g PPO resins and
The ASA resin that rubber phase acrylate content is 30~70% prepares PPO/ASA alloys and traditional weather-proof MPPO systems phase
Than, system material good toughness of the present invention, processing performance is excellent, intensity is high, weather resistance is good, composite material is environmentally friendly, and heat resistance is high,
The excellent combination property of material.
Embodiment described above is only that the preferred embodiment of the present invention is described, not to the scope of the present invention
It is defined, under the premise of design spirit of the present invention is not departed from, those of ordinary skill in the art are to technical scheme of the present invention
The various modifications made and improvement should all be fallen into the protection domain that claims of the present invention determines.
Claims (10)
1. a kind of high durable polyphenylene oxide/acrylonitrile-acrylate-styrene alloy material, which is characterized in that including following weight
The raw material components of part：
The lubricant is linear low density polyethylene.
2. alloy material according to claim 1, which is characterized in that the polyphenylene oxide resin is 30-50 parts by weight；Propylene
Nitrile-Acrylate-styrene bipolymer resin is 24-28 parts by weight；HIPS resins are 9 parts by weight.
3. alloy material according to claim 1, which is characterized in that the compatilizer is styrene/acrylonitrile copolymerization
Object graft glycidyl methacrylate, styrene-grafted maleic anhydride, ABS grafted maleic anhydrides or polyphenylene oxide grafting Malaysia
One or more of acid anhydrides.
4. alloy material according to claim 1, which is characterized in that the toughener is Styrenic block copolymerization
Object.
5. alloy material according to claim 4, which is characterized in that the styrene block copolymer be styrene-
Butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butadiene-benzene
One or more of ethylene block copolymer, styrene ethylene-propylene-styrene type block copolymer.
6. according to claim 1-5 any one of them alloy materials, which is characterized in that the inherent viscosity of the polyphenylene oxide resin
For 0.3-0.55dl/g；The melting means of the HIPS resins is 5-20g/10min (200 DEG C, 5kg), 60-150J/m.
7. according to claim 1-5 any one of them alloy materials, which is characterized in that the antioxidant is four [β-(3,5
Di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(- 4- hydroxyls -3,5 di-tert-butyl-phenyl) positive octadecyl alcolol of propionic acid
Any one of ester, phosphorous acid three (2,4 di-tert-butyl-phenyl) ester are several.
8. according to claim 1-5 any one of them alloy materials, which is characterized in that the light stabilizer is N, and N- is bis-
(2,2,2,6- tetramethyl -4- piperidyls) -1,6- hexamethylene diamines, 2-hydroxy-4-n-octoxybenzophenone or decanedioic acid double -2,2,
The one or more of 6,6- tetramethyl -4- piperidines alcohol esters.
9. according to claim 1-5 any one of them alloy materials, which is characterized in that the oxide is zinc oxide, oxygen
Change one or more of magnesium, calcium oxide；The sulfide is one or more of zinc sulphide, magnesium sulfide.
10. a kind of preparation method of high durable polyphenylene oxide/acrylonitrile-acrylate-styrene alloy material, which is characterized in that
Include the following steps：Proportioning according to claim 1 weighs each raw material, and wherein polyphenylene oxide resin is fed from the side of double screw extruder
Expect blanking, other raw materials are after mixing from the main feeding blanking of double screw extruder；The processing temperature of double screw extruder is
230~270 DEG C, screw speed is 500~600r/min, and the draw ratio of double screw extruder is 48:1.
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| CN111607216A (en) * | 2020-07-01 | 2020-09-01 | 宁波瑞隆新材料科技有限公司 | Solvent-resistant polyphenyl ether composition |
| CN114479461A (en) * | 2021-12-23 | 2022-05-13 | 广东格瑞新材料股份有限公司 | High-strength composite material capable of replacing metal material and preparation method thereof |
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